Effect of Ball-Milling Pretreatment of Cellulose on Its Photoreforming for H2 Production

Photoreforming of cellulose is a promising route for sustainable H₂ production. Herein, ball-milling (BM, with varied treatment times of 0.5–24 h) was employed to pretreat microcrystalline cellulose (MCC) to improve its activity in photoreforming over a Pt/TiO₂ catalyst. It was found that BM treatment reduced the particle size, crystallinity index (CrI), and degree of polymerization (DP) of MCC significantly, as well as produced amorphous celluloses (with >2 h treatment time). Amorphous cellulose water-induced recrystallization to cellulose II (as evidenced by X-ray diffraction (XRD) and solid-state NMR analysis) was observed in aqueous media. Findings of the work showed that the BM treatment was a simple and effective pretreatment strategy to improve photoreforming of MCC for H₂ production, mainly due to the decreased particle size and, specifically in aqueous media, the formation of the cellulose II phase from the recrystallization of amorphous cellulose, the extent of which correlates well with the activity in photoreforming.